Tert alkylphenoxy substituted polycyclic compounds

ABSTRACT

tert-Alkylphenoxy-substituted polycyclic compounds of the general formula I  
                 
 
     where  
     P is a conjugated polycyclic radical which is stable to bases and nucleophiles, optionally bears aryl substituents and contains no group from the group consisting of —CO—NH—CO—, —COOH and —CO—O—CO—;  
     R is C 1 -C 8 -alkyl, whose carbon chain may be interrupted by one or more groups selected from the group consisting of —O—, —S—, —NR 1 —, —CO— and/or —SO 2 — and which may be monosubstituted or polysubstituted by C 1 -C 6 -alkoxy or by a  5 - to  7 -membered heterocyclic radical which is attached via a nitrogen atom and may contain further heteroatoms and be aromatic;  
     C 5 -C 8 -cycloalkyl whose carbon chain may be interrupted by one or more groups selected from the group consisting of —O—, —S—, —NR 1 —, —CO— and/or —SO 2 — and which may be monosubstituted or polysubstituted by C 1 -C 6 -alkyl;  
     R 1  is hydrogen or C 1 -C 6 -alkyl;  
     Hal is chlorine and/or bromine;  
     m is from  0  to  15;    
     n is from  1  to  16 , subject to the proviso that the sum m+n is ≦ 16,    
     are prepared and used. tert-alkylphenoxy substituted polycyclic compounds of general formula (I), in which the variables have the following meanings: P=a conjugated polycyclic group, optionally aryl substituted, stable to base and acid and not containing residues from the group —CO—NH—CO—, —COOH and —CO—O—CO—; R═C1-C8 alkyl, the carbon chain of which may be interrupted by one or several groups of —O—, —S—, —NR1—, —CO— and/or —SO2— and which may be mono- or serially-substituted by C1-C6 alkoxy or 5- to 7-membered heterocyclic group, bonded by means of a nitrogen atom, which can contain further heteroatoms and can be aromatic, C5-C8 cycloalkyl. the carbon skeleton of which may be interrupted by one or several groups of —O—, —S—, —NR1—, —CO— and/or —SO2— and may optionally be substituted with C1-C6 alkyl R1═H or C1-C6 alkyl; Hal=chlorine and/or bromine; m=a number from 0 to 15; n=a number from 1 to 16, whereby the sum m+n≦16, production and use thereof.

DESCRIPTION

[0001] The present invention relates to noveltert-alkyl-phenoxy-substituted polycyclic compounds of the generalformula I

[0002] where

[0003] P is a conjugated polycyclic radical which is stable to bases andnucleophiles, optionally bears aryl substituents and contains no groupfrom the group consisting of —CO—NH—CO—, —COOH and —CO—O—CO—;

[0004] R is C₁-C₈-alkyl, whose carbon chain may be interrupted by one ormore groups selected from the group consisting of —O—, —S—, —NR¹—, —CO—and/or —SO₂— and which may be monosubstituted or polysubstituted byC₁-C₆-alkoxy or by a 5- to 7-membered heterocyclic radical which isattached via a nitrogen atom and may contain further heteroatoms and bearomatic; C₅-C₈-cycloalkyl whose carbon chain may be interrupted by oneor more groups selected from the group consisting of —O—, —S—, —NR¹—,—CO— and/or —SO₂— and which may be monosubstituted or polysubstituted byC₁-C₆-alkyl;

[0005] R¹ is hydrogen or C₁-C₆-alkyl;

[0006] Hal is chlorine and/or bromine;

[0007] m is from 0 to 15;

[0008] n is from 1 to 16, subject to the proviso that the sum m+n is 16,

[0009] and also to the preparation of these compounds and to their usefor coloring high molecular weight organic and inorganic materials, asdispersing aids and pigment additives for organic pigments, as coloringcomponent in decorative cosmetics and for preparing aqueous polymerdispersions that are colored or absorb in the ultraviolet and/or nearinfrared region of the electromagnetic spectrum.

[0010] Polycyclic organic compounds are frequently difficult toincorporate into application media because of poor solubility orcompatibility. This problem arises particularly in the case of pigments,fluorescent dyes and UV absorbers where good dispersibility in theapplication medium is essential for, respectively, color strength,fluorescence and UV protection performance.

[0011] EP-A-648 817, EP-A-648 770 and WO-A-98/32802 describe theintroduction of thermally redetachable alkoxycarbonyl substituents onthe amino and imide nitrogen atoms for reversibly solubilizing,respectively, amino- and imino-containing chromophores. However, thismethod is limited to NH-containing chromophores and generally providesuseful solubilization or compatibilization only in moderately polarmedia and only for low chromophore concentrations of <1% by weight.Moreover, the thermal fragmentation tendency of the carbamate functionprevents use in high melting thermoplastics such as polymethylmethacrylate, polyethylene terephthalate and polycarbonate. Similarlythe derivatization of diketopyrrolopyrroles with tertiary butyl groupsthat is described in DE-A-37 13 459 leads to the same limitations withregard to use levels and chromophore concentrations.

[0012] WO-A-96/22331, EP-A-227 980, WO-A-97/22607 and WO-A-96/22332disclose perylene-3,4-dicarboxylic monoimides,perylene-3,4:9,10-tetracarboxylic diimides andquaterrylene-3,4:13,14-tetracarboxylic diimides that are substituted inthe ring system by phenoxy radicals substituted by alkyl radicalscontaining up to 4 carbon atoms. These modified chromophores likewisehave adequate solubility only in application media of medium polarity.

[0013] Adv. Mater. 11, 754-758 (1999) reports the formation ofmesoscopic superstructures in organic solvents such as chloroform,carbon tetrachloride and methylcyclohexane by interaction of melaminebearing long-chain alkyl radicals with perylene- andN-(2-ethylhexyl)perylene-3,4:9,10-tetracarboxylic diimide having aryloxysubstitution in the perylene structure. The poor solubility of the1,6,7,12-tetraphenoxy-, -(p-tert-butyl)phenoxy- and-(p-tert-octyl)phenoxy-substituted perylene-3,4:9,10-tetracarboxylicdiimides that are unsubstituted on the imide nitrogen is pointed out inthis paper. The perylene derivatives described differ from the compoundsof the invention in not being base-stable because of the unsubstitutednitrogen atom.

[0014] Chem. Mater., 12, 352-362 (2000) reports the incorporation intoinorganic networks, via sol-gel processes, ofperylene-3,4:9,10-tetracarboxylic diimides and perylene-3,4-dicarboxylicimides that are alkoxysilane-modified on the imide nitrogen atoms (andhence likewise not base-stable) and in some cases additionallyaryloxy-substituted in the perylene structure. It is stated that thesolubility of the perylene derivatives can be increased by thecombination of a modification of the imide nitrogen atoms with a3-triethoxysilylpropyl group and a substitution of the perylenestructure by p-1,1,3,3-tetramethylbutylphenoxy groups.

[0015] It is an object of the present invention to provide novelpolycyclic effect materials having distinctly improved solubilitycharacteristics in both polar and nonpolar media (broadbandcompatibility) and a distinctly reduced tendency to aggregate.

[0016] We have found that this object is achieved by thetert-alkyl-phenoxy-substituted polycyclic compounds of the formula Idefined at the beginning.

[0017] The invention also provides a process for preparing the compoundsI, which comprises reacting a halide of the general formula II

[0018] in an inert basic nitrogen-containing solvent in the presence ofa base with a tert-alkylphenol of the general formula III

[0019] and if desired subsequently removing unwanted halogen.

[0020] The invention further provides for the use of the compounds I forcoloring high molecular weight organic and inorganic materials, asdispersing aids and pigment additives for organic pigments, as coloringcomponent in decorative cosmetics and also for preparing aqueous polymerdispersions that are colored or absorb in the ultraviolet and/or nearinfrared region of the electromagnetic spectrum.

[0021] The compounds of the formula I are based on a conjugatedpolycyclic radical P which is stable to bases and nucleophiles under thereaction conditions and contains no group from the group consisting of—CO—NH—CO—, —COOH and —CO—O—CO—.

[0022] P can bear further aryl substituents that are resistant to baseattack, for example unsubstituted or alkyl- and/or alkoxy-substitutedaryl, especially phenyl, or hetaryl, such as 2-, 3- and 4-pyridyl andpyrimidyl. These aryl substituents can either be attached directly tothe ring structure or else, in the case of the hereinbelow recitedpolycyclic imides, to the imide nitrogen atoms.

[0023] The tert-alkylphenoxy radical(s) in such aryl-substituted P canalso be attached to P via the aryl substituents, for example via the 4-or 3,5-positions of the phenyl radical in the case ofdiphenyldiketopyrrolopyrrole orN,N′-diphenylperylene-3,4:9,10-tetracarboxylic diimide.

[0024] Preferably P is a base-stable radical selected from the groupconsisting of naphthalenes, anthracenes, phenanthrenes, tetracenes,perylenes, terrylenes, quaterrylenes, pentarylenes, hexarylenes,anthraquinones, indanthrones, N-substituted naphthalene-1,8-dicarboxylicmonoimides (hereinafter referred to as “naphthalmonoimides” for short),N,N′-disubstituted naphthalene-1,8:4,5-tetracarboxylic diimides(“naphthalimides” for short), N-substituted perylene-3,4-dicarboxylicmonoimides (“perylmonoimides” for short), N,N′-disubstitutedperylene-3,4:9,10-tetracarboxylic diimides (“perylimides” for short),N,N′-disubstituted terrylene-3,4:11,12-tetracarboxylic diimides(“terrylimides” for short), N,N′-disubstitutedquaterrylene-3,4:13,14-tetracarboxylic diimides (“quaterrylimides” forshort), acridines, carbazoles, dibenzofurans, dinaphthofurans,benzimidazoles, benzothiazoles, phenazines, dioxazines, quinacridones,metal phthalocyanines, metal naphthalocyanines, metal porphyrins,coumarins, dibenzofuranones, dinaphtho-furanones, benzimidazolones,indigo compounds, thioindigo compounds, quinophthalones,naphthoquinophthalones and diketopyrrolopyrroles. Particular preferenceis given to P from the group consisting of naphthalenes, quinacridones,diketopyrrolopyrroles, dioxazines, indanthrones, metal phthalocyanines,metal naphthalocyanines, naphthalmonoimides, perylmonoimides,perylimides, terrylimides and quaterrylimides, and the metalphthalocyanines, metal naphthalocyanines, metal porphyrins, terrylimidesand quaterrylimides are very particularly preferred.

[0025] The tert-alkylphenoxy radicals characterizing the compounds I andalso any halogen atoms present in addition may be attached directly or,as described above, via any aryl substituents to the ring structure ofP. It will be appreciated that both forms of attachment can occur in oneand the same compound I. Relatively large P moieties, such asperylmonoimides, perylimides, terrylimides and quaterrylimides, bear thetert-alkylphenoxy radicals preferably directly on the ring structure orhave at least directly attached tert-alkylphenoxy radicals in additionto arylene-attached tert-alkylphenoxy radicals.

[0026] Depending on the size of the conjugated ring system, thecompounds I contain from at least 1 to 16 (n: 1-16), especially from 2to 8, tert-alkylphenoxy radicals.

[0027] The process of the invention introduces the tert-alkylphenoxyradicals into the compounds I by replacement of halogen. Accordingly, ifnot all the halogen atoms are replaced, the compounds I can also containup to 15 (m: 0-15), especially from 1 to 4, halogen atoms, in which casethe total number of the two substituent groups should not exceed 16,preferably 8.

[0028] Generally suitable and preferred ranges for m+n will now bementioned by way of example for particularly preferred P: naphthalenes:1-4, especially 1-2; quinacridones: 1-8, especially 2-4;diketopyrrolopyrroles: 1-6, especially 2-4; dioxazines: 1-8, especially2-4; indanthrones: 1-6, especially 2-4; metal phthalocyanines: 1-16,especially 4-8; metal naphthalocyanines: 1-16, especially 8-16;naphthalmonoimides: 1-4, especially 1-2; perylmonoimides: 1-6,especially 1-3; perylimides: 1-8, especially 2-6; terrylimides: 1-12,especially 2-8; quaterrylimides: 1-14, especially 2-8.

[0029] When P contains additional aryl substituents not used forattaching tert-alkylphenoxy, the maximum for the sum m+n decreasesaccordingly, of course.

[0030] Suitable examples of the R and R¹ radicals appearing in theformula I and also of their substituents will now be recited:

[0031] methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl,pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, 2-methylpentyl,tert-pentyl, hexyl, 2-methylpentyl, heptyl, 1-ethylpentyl, octyl,2-ethylhexyl and isooctyl;

[0032] 2-methoxyethyl, 2-ethoxyethyl, 2-propoxyethyl, 2-isopropoxyethyl,2-butoxyethyl, 2- and 3-methoxypropyl, 2- and 3-ethoxypropyl, 2- and3-propoxypropyl, 2- and 3-butoxypropyl, 2- and 4-methoxy-butyl, 2- and4-ethoxybutyl, 2- and 4-propoxybutyl, 3,6-dioxa-heptyl, 3,6-dioxaoctyl,4,8-dioxanonyl, 3,7-dioxaoctyl, 3,7-dioxanonyl, 4,7-dioxaoctyl,4,7-dioxanonyl, 2- and 4-butoxybutyl, 4,8-dioxadecyl, 3,6,9-trioxadecyland 3,6,9-trioxaundecyl;

[0033] 2-methylthioethyl, 2-ethylthioethyl, 2-propylthioethyl,2-isopropylthioethyl, 2-butylthioethyl, 2- and 3-methyl-thiopropyl, 2-and 3-ethylthiopropyl, 2- and 3-propylthiopropyl, 2- and3-butylthiopropyl, 2- and 4-methylthiobutyl, 2- and 4-ethylthiobutyl, 2-and 4-propylthiobutyl, 3,6-dithiaheptyl, 3,6-dithiaoctyl,4,8-dithianonyl, 3,7-dithiaoctyl, 3,7-dithia-nonyl, 4,7-dithiaoctyl,4,7-dithianonyl, 2- and 4-butylthiobutyl, 4,8-dithiadecyl,3,6,9-trithiadecyl and 3,6,9-trithiaundecyl;

[0034] 2-monomethyl- and 2-monoethylaminoethyl, 2-dimethylaminoethyl, 2-and 3-dimethylaminopropyl, 3-monoisopropylaminopropyl, 2- and4-monopropylaminobutyl, 2- and 4-monomethylaminobutyl,6-methyl-3,6-diazaheptyl, 3,6-dimethyl-3,6-diazaheptyl, 3,6-diazaoctyl,3,6-dimethyl-3,6-diazaoctyl, 9-methyl-3,6,9-triazadecyl,3,6,9-trimethyl-3,6,9-triazadecyl, 3,6,9-triazaundecyl and3,6,9-trimethyl-3,6,9-triazaundecyl;

[0035] propan-2-on-1-yl, butan-3-on-1-yl, butan-3-on-2-yl and2-ethyl-pentan-3-on-1-yl;

[0036] 2-methylsulfonylethyl, 2-ethylsulfonylethyl,2-propyl-sulfonylethyl, 2-isopropylsulfonylethyl, 2-butylsulfonylethyl,2- and 3-methylsulfonylpropyl, 2- and 3-ethylsulfonylpropyl, 2- and3-propylsulfonylpropyl, 2- and 3-butylsulfonylpropyl, 2- and4-methylsulfonylbutyl, 2- and 4-ethylsulfonylbutyl, 2- and4-propylsulfonylbutyl and 4-butylsulfonylbutyl;

[0037] methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy,sec-butoxy, tert-butoxy, pentoxy, isopentoxy, neopentoxy, tert-pentoxyand hexoxy;

[0038] cyclopentyl, 2- and 3-methylcyclopentyl, 2- and3-ethyl-cyclopentyl, cyclohexyl, 2-, 3- and 4-methylcyclohexyl, 2-, 3-and 4-ethylcyclohexyl, 3- and 4-propylcyclohexyl, 3- and4-isopropylcyclohexyl, 3- and 4-butylcyclohexyl, 3- and4-sec-butylcyclohexyl, 3- and 4-tert-butylcyclohexyl, cycloheptyl, 2-,3- and 4-methylcycloheptyl, 2-, 3- and 4-ethylcycloheptyl, 3- and4-propylcycloheptyl, 3- and 4-isopropylcycloheptyl, 3- and4-butylcycloheptyl, 3- and 4-sec-butylcycloheptyl, 3- and4-tert-butylcycloheptyl, cyclo-octyl, 2-, 3-, 4- and 5-methylcyclooctyl,2-, 3-, 4- and 5-ethylcyclooctyl, 3-, 4- and 5-propylcyclooctyl,2-dioxanyl, 4-morpholinyl, 2- and 3-tetrahydrofuryl, 1-, 2- and3-pyrrolidinyl and 1-, 2-, 3- and 4-piperidyl.

[0039] Examples of preferred tert-alkoxyphenoxy radicals arep-(1,1-dimethylpropyl)phenoxy, p-(1,1-dimethylbutyl)phenoxy,p-(1,1-dimethylpentyl)phenoxy, p-(1,1,3,3-tetra-methylbutyl)phenoxy,p-(2-cyclopentyl-1,1-dimethylethyl)phenoxy,p-(2-cyclohexyl-1,1-dimethylethyl)phenoxy,p-(2-cycloheptyl-1,1-dimethylethyl)phenoxy andp-(1,1-dimethyl-2-(4-morpholinyl)-ethyl)phenoxy.

[0040] The particularly preferred naphthalmonoimides, perylmonoimides,perylimides, terrylimides and quaterrylimides bear in particular thefollowing base-stable substituents on the imide nitrogen atoms:

[0041] C₆-C₃₀-alkyl whose carbon chain may be interrupted by one or moregroups selected from the group consisting of —O—, —S—, —NR¹—, —CO—and/or —SO₂— and which may be monosubstituted or polysubstituted byC₁-C₆-alkoxy or by a 5- to 7-membered heterocyclic radical which isattached via a nitrogen atom and may contain further heteroatoms and bearomatic;

[0042] C₅-C₈-cycloalkyl whose carbon chain may be interrupted by one ormore groups selected from the group consisting of —O—, —S—, —NR¹—, —CO—and/or —SO₂— and which may be monosubstituted or polysubstituted byC₁-C₆-alkyl;

[0043] aryl or hetaryl which may each be monosubstituted orpolysubstituted by C₁-C₁₈-alkyl, C₁-C₆-alkoxy, cyano, —CONH—R¹ and/or—NH—COR¹.

[0044] The following radicals may be specifically mentioned by way ofexample for these substituents in addition to the radicals alreadymentioned:

[0045] nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tridecyl,isotridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl,nonadecyl and eicosyl (the designations, isononyl, isodecyl andisotridecyl as well as the above-mentioned designation isooctyl aretrivial names derived from the alcohols obtained by the oxo process);

[0046] 3,6,9-trioxadodecyl, 3,6,9,12-tetraoxatridecyl and3,6,9,12-tetraoxatetradecyl; 3,6,9-trithiadodecyl,3,6,9,12-tetrathiatridecyl and 3,6,9,12-tetrathiatetradecyl;

[0047] carbamoyl, methylaminocarbonyl, ethylaminocarbonyl,propylaminocarbonyl, butylaminocarbonyl, pentylaminocarbonyl,hexylaminocarbonyl, heptylaminocarbonyl, octylaminocarbonyl,nonylaminocarbonyl and decylaminocarbonyl; formylamino, acetylamino andpropionylamino;

[0048] 2-, 3- and 4-methylphenyl, 2,4-, 2,5-, 3,5- and2,6-dimethylphenyl, 2,4,6-trimethylphenyl, 2-, 3- and 4-ethylphenyl,2,4-, 2,5-, 3,5- and 2,6-diethylphenyl, 2,4,6-triethylphenyl, 2-, 3- and4-propylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dipropylphenyl,2,4,6-tripropylphenyl, 2-, 3- and 4-isopropylphenyl, 2,4-, 2,5-, 3,5-and 2,6-diisopropylphenyl, 2,4,6-triisopropylphenyl, 2-, 3- and4-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-dibutylphenyl,2,4,6-tributylphenyl, 2-, 3- and 4-isobutylphenyl, 2,4-, 2,5-, 3,5- and2,6-diisobutylphenyl, 2,4,6-triisobutylphenyl, 2-, 3- and4-sec-butylphenyl, 2,4-, 2,5-, 3,5- and 2,6-di-sec-butylphenyl,2,4,6-tri-sec-butylphenyl, 2-, 3- and 4-tert-butylphenyl, 2,4-, 2,5-,3,5- and 2,6-di-tert-butylphenyl and 2,4,6-tri-tert-butylphenyl; 2-, 3-and 4-methoxyphenyl, 2,4-, 2,5-, 3,5- and 2,6-dimethoxyphenyl,2,4,6-trimethoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-, 2,5-, 3,5- and2,6-diethoxyphenyl, 2,4,6-triethoxyphenyl, 2-, 3- and 4-propoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-dipropoxyphenyl, 2-, 3- and 4-isopropoxyphenyl,2,4-, 2,5-, 3,5- and 2,6-diisopropoxyphenyl and 2-, 3- and4-butoxyphenyl; 2-, 3- and 4-cyanophenyl; 3- and 4-carboxamidophenyl, 3-and 4-N-(methyl)carboxamidophenyl and 3- and4-N-(ethyl)carboxamidophenyl; 3- and 4-acetylaminophenyl, 3- and4-propionylaminophenyl and 3- and 4-butyrylaminophenyl.

[0049] The inventive compounds I are advantageously preparable by thesimilarly inventive process by reacting the corresponding halides of theformula II with tert-alkylphenols of the formula III in an inert basicnitrogen-containing solvent in the presence of a base and if desiredsubsequently removing unwanted halogen.

[0050] Useful inert basic nitrogen-containing solvents are in particularpolar solvents, especially nitrogen-containing heterocycles, such aspyridine, pyrimidine, quinoline, isoquinoline, quinaldine and preferablyN-methylpyrrolidone, and also carboxamides, such asN,N-dimethylformamide and N,N-dimethylacetamide.

[0051] The solvent quantity depends on the solubility of the halide IIand is customarily in the range from 2 to 40 g, preferably from 4 to 25g, of solvent per g of halide II.

[0052] Useful bases are in particular nonnucleophilic or only weaklynucleophilic compounds. Examples of such bases are alkali metalhydroxides, such as potassium hydroxide and sodium hydroxide, alkalimetal carbonates, such as potassium carbonate and sodium carbonate, andalso alkali metal alkoxides of tertiary alcohols, such as lithiumtert-butoxide, sodium tert-butoxide and potassium tert-butoxide, whichare used in anhydrous form.

[0053] In general, from 0.8 to 1.5, preferably from 1.0 to 1.2, molequivalents of base are used per mole of halogen atom to be replaced.

[0054] The halides II used as starting materials are generally known orobtainable according to known methods by reacting the unhalogenatedconjugated polycyclic compounds with halogenating agents, especially theelemental halogens. Such halides II that contain halogen atoms attachedto aryl substituents are known to be generally obtainable byintroduction of the halogenated aryl radicals into the polycyclicsystem.

[0055] The molar ratio of halide II to phenol III depends on the numberof halogen atoms to be replaced. In general, from 1 to 2, preferablyfrom 1 to 1.3, mol of phenol III is used per mole of halogen atom to bereplaced in halide II.

[0056] The reaction temperature is customarily in the range from 50 to200° C., preferably at from 60 to 140° C.

[0057] It is advisable for the reaction to be carried out underprotective gas, for example nitrogen or argon.

[0058] The reaction time depends on the reactivity of the halide II andis about 2-48 h.

[0059] Varying the reaction conditions—amount of phenol III and base andthe reaction temperature—advantageously provides control over thehalogen replacement, so that it is no problem to prepare not onlyproducts I where all the halogen atoms have been replaced (m=0) but alsoproducts I which do contain halogen. If desired, the halogen cansubsequently be removed from the product I. Thus, a single startingmaterial II can be used, if desired, to prepare various products I.

[0060] The process is advantageously carried out by initially chargingthe solvent, adding halide II, phenol III and base and heating theresulting solution or suspension to the desired reaction temperature for2-48 h while stirring under protective gas.

[0061] After cooling down to room temperature, the reaction product canbe isolated by filtering off the precipitated reaction product directlyor after dilution with 3 to 4 times the volume of water, a diluteinorganic acid, for example 5-10% by weight hydrochloric acid, or analiphatic alcohol, for example methanol, washing first with a littlesolvent and then with water to neutral run-off and drying under reducedpressure.

[0062] In some cases, especially when the bromides II, which are morebase-labile and hence more prone to undesirable secondary reactions, areto be used to provide high degrees of substitution n, it can beadvantageous, for achieving high product purity, for the phenoxylationreaction to be carried out in two stages. In this case, the halide II isinitially reacted with only a portion, advantageously the amount neededto replace the most labile halogen substituents, of phenol III and base,the partially phenoxylated product is separated from the reactionmixture by filtration and is subsequently reacted with the rest ofphenol III and base to form the desired product.

[0063] In general, the compounds I obtained according to the inventionhave a sufficiently high assay (>95%) that there is no need for furtherpurification. Analytically pure products can be prepared byrecrystallization from aromatic solvents, such as toluene and xylene, orhalogenated hydrocarbons, such as methylene chloride and chloroform, orby filtration of a solution of the products in these solvents throughsilica gel and subsequent concentrating.

[0064] If only part of the halogen substituents was replaced and thehalogen atoms still present are to be removed, this can be done by meansof known methods.

[0065] By way of example, two dehalogenations will now be describedwhich would be very advantageous for this purpose.

[0066] In the first method, the dehalogenation is base-induced in thepresence of an inert basic nitrogen-containing or aromatic solvent.

[0067] Useful bases for this purpos include for example alkali metalhydroxides, such as potassium hydroxide and sodium hydroxide, alkalimetal carbonates, such as potassium carbonate and sodium carbonate,alkali metal alkoxides of secondary and tertiary alcohols such aslithium isopropoxide, sodium isopropoxide, potassium isopropoxide,lithium tert-butoxide, sodium tert-butoxide and potassium tert-butoxide,and also sterically hindered nitrogen bases, such as diazabicyclooctane(DABCO), diazabicyclononene (DBN) and diazabicycloundecene (DBU).

[0068] The amount of base is not critical as such. It is customary touse from 1 to 3, preferably from 1 to 1.5, mol equivalents of base permole of halogen atom to be eliminated.

[0069] Useful solvents include not only aromatic solvents, such astoluene and xylene, but also the same solvents as used in thephenoxylation, the use level of which in turn depends on the solubilityof the compound I to be dehalogenated and is generally in the range from2 to 50 g, preferably in the range from 5 to 25 g, per g of compound I.

[0070] The reaction temperature is customarily in the range from 50 to200° C., preferably at from 60 to 130° C.

[0071] It is advisable for the dehalogenation to be carried out underprotective gas, for example nitrogen or argon.

[0072] The reaction time depends on the reactivity of the compound I tobe dehalogenated and is about 1-6 h.

[0073] The process is advantageously carried out by initially charging asolution or suspension in the solvent of the compound I to bedehalogenated, adding the base and heating the resulting mixture to thedesired reaction temperature for 1-6 h while stirring under protectivegas. When there is a risk of undesirable secondary reactions, forexample saponifications, it is advantageous for the base not to be addeduntil after the heating to reaction temperature.

[0074] After cooling down to room temperature, the reaction product canbe isolated by diluting the reaction mixture with from 3 to 4 times thevolume of a dilute inorganic acid, for example 5-10% by weighthydrochloric acid, filtering off the thusly precipitated product,washing initially with the dilute acid and then with methanol or waterto neutral run-off and drying under reduced pressure.

[0075] The second method comprises a transition metal catalyzedreductive dehalogenation in the presence of a solvent that is inertunder the reaction conditions.

[0076] The reducing agents used here are preferably complex hydrides,especially aluminohydrides, such as lithium aluminohydride, andespecially borohydrides, preferably sodium borohydride, or elementalhydrogen.

[0077] The amount of reducing agent is not critical as such. Generallyfrom 1 to 5, preferably from 2 to 3, mol equivalents of reducing agentare used per mole of halogen atom to be eliminated.

[0078] Useful transition metal catalysts include in particular palladiumcompounds, such as Pd(II) and Pd(0) compounds. The reduction withcomplex hydrides is preferably catalyzed using palladium(II) acetate,dichloro(1,5-cyclooctadiene)palladium(II),dichloro[1,1′-bis(diphenylphosphino)ferrocene]palladium(II),tris(dibenzylideneacetone)dipalladium(0),tetrakis(triphenyl-phosphine)palladium(0) andtetrakis(tris-o-tolylphosphine)-palladium(0) and the reduction withelemental hydrogen is preferably catalyzed using palladium-dopedactivated carbon.

[0079] Generally from 0.5 to 2 mol % of catalyst are used per mole ofhalogen atom to be eliminated.

[0080] The choice of solvent depends on the choice of reducing agent.When complex hydrides are used, it is especially polar aprotic solvents,such as aliphatic and cycloaliphatic ethers, aromatic solvents andaliphatic nitrites, which are suitable, while it is especially aliphaticalcohols which are suitable if elemental hydrogen is used.

[0081] Specific examples of these solvents are diethyl ether,tetrahydrofuran and dioxane, toluene and xylene, acetonitrile, which isused with borohydrides in particular, and also methanol and ethanol.

[0082] The amount of solvent is determined by the solubility of thecompound I to be dehalogenated and is generally in the range from 2 to50 g, preferably in the range from 5 to 25 g, per g of compound I.

[0083] The reaction temperature is customarily in the range from 0 to150° C., preferably in the range from 20 to 100° C., although thereduction with complex hydrides is generally carried out at highertemperatures (about 50-100° C.) than the reduction with elementalhydrogen.

[0084] When complex hydrides are used as reducing agents, it isadvisable to work under protective gas. A hydrogenation with elementalhydrogen is advantageously performed under a small hydrogenoverpressure.

[0085] Depending on the reactivity of compound I, the dehalogenationtakes from 4 to 72 h.

[0086] The process for dehalogenating with complex hydrides isadvantageously carried out by initially charging the solvent, adding thecompound I to be dehalogenated and the hydride, and heating theresulting solution or suspension to the desired reaction temperature for4-72 h while stirring under protective gas.

[0087] After cooling down to room temperature and destroying excesshydride by addition of water, the reaction product can be isolated asdescribed for the base-induced dehalogenation.

[0088] The process for dehalogenating with elemental hydrogen isadvantageously carried out by initially charging a hydrogenation reactorwith a suspension, in the solvent, of the compound I to be dehalogenatedand the catalyst and heating to the reaction temperature for 4-72 hwhile stirring under a small hydrogen overpressure (about 0.1-0.5 bar).

[0089] After cooling down to room temperature, depressurizing anddisplacing excess hydrogen with nitrogen, the reaction product can beisolated as already described.

[0090] To produce compounds I having a >95% assay, the as-dehalogenatedcompounds can be subjected to a purification step. Useful purificationoptions include for example fractional crystallization from solventmixtures with an aromatic solvent, such as toluene and xylene, or ahalogenated hydrocarbon, such as methylene chloride, chloroform and1,1,2,2-tetrachloroethane, as one component and an extremely nonpolarsolvent, such as pentane or hexane, as the other component or columnchromatography over silica gel using these solvent mixtures as mobilephase.

[0091] The compounds I according to the invention are notable for theirhigh solubility in, ie. their very good compatibility with, not onlypolar media (eg. aliphatic alcohols and esters on the one hand andpolyacrylates, polycarbonates and polyesters on the other) but alsononpolar media (respectively alkanes and polyolefins, for example).

[0092] They may be used with advantage for a multiplicity ofapplications, for example for coloring or additivating high molecularweight organic and inorganic materials, especially plastics, paints andprinting inks, and oxidic materials, such as low temperature ceramicsand pigments based on metal oxides, specifically multilayer interferencepigments containing metal oxides as individual layers, as dispersingaids and pigment additive for organic pigments, as coloring component indecorative cosmetics and also for preparing aqueous polymer dispersionsthat are colored or absorb in the UV and/or NIR, in which case theprocess described in WO-A-99/40123 may be employed in particular.

[0093] Applications where a compound I is desired that is colored, ie.that absorbs in the visible region of the electromagnetic spectrum, areusefully implemented using in particular such compounds I as contain a Pfrom the group consisting of perylenes, terrylenes, quaterrylenes,pentarylenes, hexarylenes, indanthrones, perylmonoimides, perylimides,terrylimides, dinaphthofurans, dioxazines, quinacridones, metalphthalocyanines, metal porphyrins, coumarins, dinaphthofuranones, indigocompounds, thioindigo compounds, quinophthalones, naphthoquinophthalonesand diketopyrrolopyrroles.

[0094] Applications requiring a compound I that is colorless or onlyweakly colored, absorbing in the ultraviolet and/or near infrared regionof the electromagnetic spectrum, for example additivating high molecularweight organic and inorganic materials, as dispersing aids for organicpigments and also for preparing aqueous polymer dispersions that absorbin the UV and/or NIR, are usefully implemented using in particular suchcompounds I as contain a P from the group consisting of naphthalenes,anthracenes, phenanthrenes, tetracenes, anthraquinones,naphthalmonoimides, naphthalimides, quaterrylimides, acridines,carbazoles, dibenzofurans, benzimidazoles, benzothiazoles, phenazines,metal naphthalocyanines, dibenzofuranones and benzimidazolones.

[0095] Useful pigment additives for organic pigments include not onlythe colorless or only weakly colored compounds I, but also coloredcompounds I whose self-color is substantially coincident with theself-color of the pigments to be additivated.

EXAMPLES

[0096] A) Preparation of Compounds I According to the Invention Examples1 to 9

[0097] A mixture of x g (20 mmol) of halide II, y g of tert-alkylphenolIII, z g of base B and a ml of N-methylpyrrolidone was heated to T°C fort h while stirring in a nitrogen atmosphere.

[0098] After cooling down to room temperature, the precipitated reactionproduct was filtered off either directly (Example 6) or after dilutionwith three times the volume of methanol (Examples 1 to 3), water(Example 8) or 5% by weight hydrochloric acid (Examples 4, 5, 7 and 9)and washed with water to neutral run-off. In the case of Examples 1 to 3on the one hand and 6 on the other, the filter residue was previouslywashed with, respectively, a little methanol or a littleN-methylpyrrolidone. In the case of Examples 6 and 7 a column filtrationwith methylene chloride as mobile phase was additionally carried out.The final drying was carried out in all cases at 100° C. under reducedpressure.

[0099] This reaction led in all examples to the complete replacement ofthe halogen atoms by the tert-alkylphenoxy radicals.

[0100] Further details concerning these experiments and their resultsare summarized in Table 1. The yield in g is the total yield, while theyield in % is based on the desired phenoxylation product.

[0101] Table 1 uses the following designations: TABLE 1 x Hal. yAlkylphenol z Base a t T Yield Ex. [g] II [g] III [g] B [ml] [h] [° C.][g]/[%] Appearance 1 14.4 IIa 13.6 p-t-octylphenol 4.55 potassium 150 690 18.8/−* dark red, carbonate microcrystalline 2 17.0 IIb 21.5p-t-octylphenol 6.1 potassium 150 15 90 22.0/72 deep red, carbonatemicrocrystalline 3 17.0 IIb 24.2 p-(2-cyclohexyl- 6.1 potassium 150 1290 24.8/76 dark red, 1,1-dimethyl- carbonate crystalline ethyl)phenol 417.4 IIc 9.1 p-t-octylphenol 3.3 potassium 175 15 100 19.7/88 dark red,carbonate crystalline 5 17.7 IId 9.1 p-t-octylphenol 3.3 potassium 20015 100 18.6/82 brownish red, carbonate microcrystalline 6 28.6 IIe 32.2p-t-octylphenol 9.95 potassium 150 10 95 31.0/71** light green,carbonate amorphous 7 28.6 IIe 32.2 p-t-octylphenol 13.5 potassium 200 480 28.0/64** light green, t-butoxide amorphous 8 10.2 IIf 10.3p-t-octylphenol 3.05 potassium 250 48 100  5.6/74*** bluish green,carbonate microcrystalline 9 10.0 IIg 30.0 p-t-octylphenol 7.0 potassium100 48 140  8.4/64 bluish green, carbonate amorphous

EXAMPLE 10

[0102] Example 6 was repeated to react 28.6 g of a 1:1 mixture ofN,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,18-hexabromo-quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,19-hexabromo-quaterrylene-3,4:13,14-tetracarboxylicdiimide with 20.6 g of p-tert-octylphenol and 6.9 g of potassiumcarbonate.

[0103] This afforded 27.6 g of a 1:1 mixture ofN,N′-bis(2,6-diiso-propylphenyl)-8,18-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-8,19-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetra-carboxylicdiimide in the form of a dark green crystalline powder, whichcorresponds to a yield of 71%.

[0104] In addition, the N-methylpyrrolidone mother liquor was dilutedwith four times the amount of a 1:1 mixture of methanol and water toafford 11 g (yield 25%) of the 1:1 mixture ofN,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,18-hexa(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,19-hexa(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide of Example 6.

EXAMPLE 11

[0105] 38.7 g of the 1:1 mixture ofN,N′-bis(2,6-diisopropyl-phenyl)-8,18-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-8,19-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetra-carboxylicdiimide were reacted with 10.7 g of p-tert-octylphenol and 3.32 g ofpotassium carbonate in 170 ml of N-methyl-pyrrolidone similarly toExample 6, except that the reaction time was extended to 18 h.

[0106] This afforded 39.5 g of a 1:1 mixture ofN,N′-bis(2,6-diiso-propylphenyl)-1,6,8,11,16,18-hexa(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-1,6,8,11,16,19-hexa(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide in the form of a light green amorphous powder having a residualbromine content <0.05% by weight, which corresponds to a yield of 90%.

EXAMPLE 12

[0107] The 1:1 mixture ofN,N′-bis(2,6-diisopropylphenyl)-8,18-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide andN,N′-bis(2,6-diisopropylphenyl)-8,19-dibromo-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetra-carboxylicdiimide of Example 10 (hereinafter designated “Ia”) was converted bydehalogenation intoN,N′-bis(2,6-diisopropylphenyl)-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetra-carboxylicdiimide. The dehalogenation was conducted according to the followingmethods:

[0108] a) A mixture of 38.7 g of Ia and 600 ml of N-methylpyrrolidonewas stirred under nitrogen and heated to 130° C., admixed with 6.75 g ofpotassium tert-butoxide and maintained at 130° C. for 1.5 h.

[0109] After cooling down to room temperature, the reaction product wasprecipitated by adding the reaction mixture to 21 of 5% by weighthydrochloric acid, filtered off, washed first with 5% by weighthydrochloric acid to colorless run-off and then with water to neutralrun-off and dried at 100° C. under reduced pressure. The isolatedreaction product was then subjected to column chromatography over silicagel using 1:1 toluene/hexane as mobile phase.

[0110] This afforded 20.0 g ofN,N′-bis(2,6-diisopropyl-phenyl)-1,6,11,16-tetra(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide in the form of a light green amorphous powder having a UV/VISspectroscopic purity of >99% and a residual bromine content <0.01%,which corresponds to a yield of 56%.

[0111] b) Example 12a) was repeated, except that 4.1 g of potassiumcarbonate was used as base instead of potassium tert-butoxide. Theworkup and purification were likewise carried out similarly to Example12a).

[0112] This afforded 18.6 g ofN,N′-bis(2,6-diisopropylphenyl)-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide in the form of a light green amorphous powder having a purityof >99.5% and a residual bromine content of 0.00%, which corresponds toa yield of 52%.

[0113] c) A mixture of 38.7 g of Ia, 3.8 g of sodium borohydride, 0.46 gof tetrakis(triphenylphosphine)palladium(0) and 600 ml of dioxane washeated to 60° C. for 48 h while stirring in a nitrogen atmosphere.

[0114] After cooling down to room temperature, excess hydride wasdecomposed by gradual addition of 10 ml of water. The rest of the workupand purification was carried out similarly to Example 12a).

[0115] This afforded 21.7 g ofN,N′-bis(2,6-diisopropyl-phenyl)-1,6,11,16-tetra(p-tert-octylphenoxy)-quaterrylene-3,4:13,14-tetracarboxylicdiimide in the form of a light green amorphous powder having a purityof >99% and a residual bromine content of 0.00%, which corresponds to ayield of 61%.

[0116] d) A mixture of 38.7 g of Ia, 3.8 g of sodium borohydride, 0.23 gof tetrakis(triphenylphosphine)palladium(0) and 1000 ml of acetonitrilewas heated to 69° C. for 25 h while stirring in a nitrogen atmosphere.

[0117] After cooling down to room temperature, excess hydride wasdecomposed by gradual addition of 10 ml of water. The rest of the workupand purification was carried out similarly to Example 12a).

[0118] This afforded 29.1 g ofN,N′-bis(2,6-diisopropyl-phenyl)-1,6,11,16-tetra(p-tert-octylphenoxy)quaterrylene-3,4:13,14-tetracarboxylicdiimide in the form of a light green amorphous powder having a purityof >99% and a residual bromine content of 0.00%, which corresponds to ayield of 82%.

EXAMPLE 13

[0119] a) A mixture of 20.85 g (25 mmol) ofN,N′-bis(2,6-diisopropyl-phenyl)terrylene-3,4:11,12-tetracarboxylicdiimide, 20 g (125 mmol) of bromine and 1250 ml of chloroform wasrefluxed for 12 h in the dark with stirring. The reaction solution wascooled down to room temperature, the solvent was stripped off underreduced pressure, and the crude product was chromatographed over silicagel using dichloromethane as mobile phase.

[0120] This afforded 22.5 g ofN,N′-bis(2,6-diisopropylphenyl)-1,6,9,14-tetrabromoterrylene-3,4:11,12-tetracarboxylicdiimide in the form of a blue crystalline solid having a meltingpoint >300° C., which corresponds to a yield of 78%.

[0121] Analytical data:

[0122] elemental analysis (% by weight, calculated/observed): C:60.55/60.7, H: 3.7/3.7, N: 2.45/2.45, 0: 5.55/5.6, Br: 27.75/27.55,

[0123] mass (FD, 8 kV): m/z=1145.3 (M⁺, 100%),

[0124] IR (KBr): ν=1703 (s, C═O), 1660 (s, C═O) cm⁻¹,

[0125] UV/VIS (CHCl₃): λ_(max) (ε)=559 (15850), 605 (46770), 656 (93330)nm.

[0126] b) A mixture of 11.5 g (10 mmol) ofN,N′-bis(2,6-diisopropyl-phenyl)-1,6,9,14-tetrabromoterrylene-3,4:11,12-tetra-carboxylicdiimide, 10.3 g (50 mmol) of p-tert-octylphenol, 3.45 g (25 mmol) ofpotassium carbonate and 250 ml of N-methylpyrrolidone was heated to 80°C. under nitrogen for 8 h with stirring. The reaction mixture was cooleddown to room temperature and diluted with three times the volume of 5%by weight hydrochloric acid, and the precipitated reaction product wasfiltered off, washed neutral with water, dried and subjected to columnfiltration over silica gel using methylene chloride as mobile phase.

[0127] This afforded 13.2 g ofN,N′-bis(2,6-diisopropylphenyl)-1,6,9,14-tetra(p-tert-octylphenoxy)terrylene-3,4:11,12-tetra-carboxylicdiimide in the form of a dark blue crystalline solid having a meltingpoint >300° C., which corresponds to a yield of 80%.

[0128] Analytical data:

[0129] elemental analysis (% by weight, calculated/observed): C:82.85/82.8, H: 7.7/7.7, N: 1.7/1.7, 0: 7.75/7.8,

[0130] mass (FD, 8 kv): m/z=1651.2 (M⁺, 100%),

[0131] IR (KBr): ν=1708 (s, C═O), 1668 (s, C═O) cm⁻¹,

[0132] UV/VIS (CHCl₃): λ_(max) (ε)=628 (52930), 669 (128770) nm.

Example 14

[0133] a) Example 13a) was repeated, except that a mixture of 18.9 g (25mmol) ofN-cyclohexyl-N′-(2,6-diisopropylphenyl)-terrylene-3,4:11,12-tetracarboxylicdiimide, 20 g (125 mmol) of bromine and 1250 ml of chloroform was used.

[0134] This afforded 19.8 g ofN-cyclohexyl-N′-(2,6-diisopropyl-phenyl)-1,6,9,14-tetrabromoterrylene-3,4:11,12-tetra-carboxylicdiimide in the form of a blue microcrystalline solid having a meltingpoint >300° C., which corresponds to a yield of 74%.

[0135] Analytical data:

[0136] elemental analysis (% by weight, calculated/observed): C:58.25/58.35, H: 3.4/3.4, N: 2.6/2.6, 0: 5.95/6.0, Br: 29.8/29.65,

[0137] mass (FD, 8 kV): m/z=1073.0 (M+, 100%),

[0138] IR (KBr): ν=1705 (s, C═O), 1662 (s, C═O) cm⁻¹,

[0139] UV/VIS (CHCl₃): λ_(max) (ε)=556 (16790), 600 (48290), 652 (90070)nm.

[0140] b) Example 13b) was repeated, except that a mixture of 10.7 g (10mmol) ofN-cyclohexyl-N′-(2,6-diisopropylphenyl)-1,6,9,14-tetrabromoterrylene-3,4:11,12-tetracarboxylicdiimide, 10.3 g (50 mmol) of p-tert-octylphenol, 3.45 g (25 mmol) ofpotassium carbonate and 250 ml of N-methylpyrrolidone was used and thecrude product was subjected to column filtration using dichloromethane.

[0141] This afforded 12.9 g ofN-cyclohexyl-N′-(2,6-diisopropyl-phenyl)-1,6,9,14-tetra(p-tert-octylphenoxy)terrylene-3,4:11,12-tetracarboxylic diimide in the form of a dark blue crystallinesolid having a melting point >300° C., which corresponds to a yield of82%.

[0142] Analytical data:

[0143] elemental analysis (% by weight, calculated/observed): C:85.9/85.8, H: 8.2/8.3, N: 1.8/1.8, 0: 4.1/4.1,

[0144] mass (FD, 8 kV): m/z=1565.3 (M⁺, 100%),

[0145] IR (KBr): 84 =1709 (s, C═O), 1667 (s, C═O) cm⁻¹,

[0146] UV/VIS (CHCl₃): λ_(max) (ε)=624 (54010), 667 (129770) nm.

[0147] B) Evaluation and use of compounds I according to the invention

Example 15

[0148] The solubility of the compounds I prepared in Examples 1 to 14was evaluated in extremely nonpolar to polar solvents. Generally, adistinctly improved solubility was observed compared to the compoundswithout tert-alkylphenoxy substitution. Details relating to theseexperiments are listed in Table 2.

[0149] The solubility of these compounds I was at least 10% by weightalso in molten polystyrene, polymethyl methacrylate and polycarbonate.TABLE 2 Solubility [g/l] in Compound I Pentane Toluene Isopropanol ofEx. (25° C.) (25° C.) (50° C.)  1 53 >250 56  2 81 >400 92  3 65 >350 87 4 55 >250 59  5 24 155 47  6 55 >500 49  7 55 >500 49  8 12 88 10 12a51 unlimited 48 12b 51 unlimited 48 12c 51 unlimited 48 13b 75 unlimited56 14b 72 unlimited 52

EXAMPLE 16

[0150] Example 25 of WO-A-99/40123 was repeated to prepare aqueouspolymer dispersions containing 15% by weight of the fluorescent colorantof Example 2 or 10/25% by weight of the near infrared absorber ofExample 6 in homogeneous dispersion. The correspondingphenoxy-substituted derivatives, by contrast, were only incorporablewith homogeneous results up to a concentration of respectively 7 and 1%by weight.

We claim:
 1. tert-Alkylphenoxy-substituted polycyclic compounds of thegeneral formula I

where P is a conjugated polycyclic radical which is stable to bases andnucleophiles, optionally bears aryl substituents and contains no groupfrom the group consisting of —CO—NH—CO—, —COOH and —CO—O—CO—; R isC₁-C₈-alkyl, whose carbon chain may be interrupted by one or more groupsselected from the group consisting of —O—, —S—, —NR¹—, —CO— and/or —SO₂-and which may be monosubstituted or polysubstituted by C₁-C₆-alkoxy orby a 5- to 7-membered heterocyclic radical which is attached via anitrogen atom and may contain further heteroatoms and be aromatic;C₅-C₈-cycloalkyl whose carbon chain may be interrupted by one or moregroups selected from the group consisting of —O—, —S—, —NR¹—, —CO—and/or —SO₂- and which may be monosubstituted or polysubstituted byC₁-C₆-alkyl; R¹ is hydrogen or C₁-C₆-alkyl; Hal is chlorine and/orbromine; m is from 0 to 15; n is from 1 to 16, subject to the provisothat the sum m+n is ≦16.
 2. Compounds as claimed in claim 1 of theformula I where P is a base-stable radical selected from the groupconsisting of naphthalenes, anthracenes, phenanthrenes, tetracenes,perylenes, terrylenes, quaterrylenes, pentarylenes, hexarylenes,anthraquinones, indanthrones, N-substituted naphthalene-1,8-dicarboxylicmonoimides, N,N′-disubstituted naphthalene-1,8: 4,5-tetracarboxylicdiimides, N-substituted perylene-3,4-dicarboxylic monoimides,N,N′-disubstituted perylene-3,4:9,10-tetracarboxylic diimides,N,N′-di-substituted terrylene-3,4:11,12-tetracarboxylic diimides,N,N′-disubstituted quaterrylene-3,4:13,14-tetracarboxylic diimides,acridines, carbazoles, dibenzofurans, dinaphtho-furans, benzimidazoles,benzothiazoles, phenazines, dioxazines, quinacridones, metalphthalocyanines, metal naphthalocyanines, metal porphyrins, coumarins,dibenzo-furanones, dinaphthofuranones, benzimidazolones, indigocompounds, thioindigo compounds, quinophthalones,naphtho-quinophthalones and diketopyrrolopyrroles.
 3. A process forpreparing compounds of the general formula I as set forth in claim 1 or2, which comprises reacting a halide of the general formula II

in an inert basic nitrogen-containing solvent in the presence of a basewith a tert-alkylphenol of the general formula III

and if desired subsequently removing unwanted halogen.
 4. The use ofcompounds of the general formula I as set forth in claim 1 or 2 forcoloring high molecular weight organic and inorganic materials.
 5. Theuse of claim 4, wherein plastics, paints and printing inks are colored.6. The use of compounds of the general formula I as set forth in claim 1or 2 as dispersing aids and pigment additives for organic pigments. 7.The use of compounds of the general formula I as set forth in claim 1 or2 as coloring component in decorative cosmetics.
 8. The use of compoundsof the general formula I as set forth in claim 1 or 2 for preparingaqueous polymer dispersions that are colored or absorb in theultraviolet and/or near infrared region of the electromagnetic spectrum.